Triorganostannoxy zirconium alcohol ate derivatives of dialkanolamine



United States Patent 3,431,288 TRIORGANOSTANNOXY ZIRCONIUM ALCOHOL- ATEDERIVATIVES 0F DIALKANOLAMINE Ambrose J. Gibbons, Jr., Catonsville, Md.and Richard E. De Marco, Waldwick, N.J., assignors, by mesneassignments, to SCM Corporation, New York, N.Y., a corporation of NewYork No Drawing. Original application Nov. 10, 1964, Ser. No. 410,295,now Patent No. 3,361,775, dated Jan. 2, 1968. Divided and thisapplication Apr. 24, 1967, Ser. No. 632,922

US. Cl. 260-4293 2 Claims Int. Cl. C07f 7/22, 7/00 ABSTRACT OF THEDISCLOSURE Novel stannoxy zirconium compounds have been presented in US.patent application S.N. 410,295, filed Nov. 10, 1964, now US. Patent No.3,361,775. Presented in this application are derivatives of suchstannoxy zirconium compounds wherein attachment of one or more of theacyloxy or alkoxy radicals on the zirconiurn atom is replaced bydialkanolamine residue such as the residue from diethanolamine. Thecompounds are useful as agents for conferring water repellancy to porousmaterials, as catalysts for organic reactions and they exhibitfungicidal properties.

This application is a division of US. patent application S.N. 410,295,filed Nov. 10, 1964, entitled, Triorganostannoxy ZirconiumTrialcoholates and Derivatives.

This invention relates to novel compounds in which the characterizinglinkage is ESn-OZrE or (ESnO--) Zr=. The three valences of the tin inthese linkages can be satisfied with a variety of alike or differentmonovalent hydrocarbyl groups such as alkyl, alkenyl, alkynyl, aryl,alkaryl, aralkyl, cycloaliphatic and like groups containing 1-12carbons. The two or three valences of the zirconium in saidcharacterizing linkages can be satisfied with a variety of alike ordifferent -OR groups or groups wherein R can be any alkyl or fluoroalkylgroup of 1-18 carbons.

The novel compounds are useful as agents conferring water-repellancy toporous mate-rials such as cloth, paper, concrete, wood, asbestos-cementarticles, ceramics, "and the like. They also exhibit fungicidalproperties, and in addition function well as catalysts for a variety oforganic reactions, e.g., as curing catalysts for urethane foams.

Accordingly, it is an object of this invention to provide novelcompounds, characterized by the linkage A further object is to provideporous articles which have been rendered water-repellant by treatmentwith one or more of said novel compounds.

Another object is to provide articles which have been renderedbacteriostatic by treatment with said novel compounds.

A further object is to provide improved urethane foams through the useof one or more of said novel compounds as curing catalyst(s).

These and related objects will be understood from the foregoing andfollowing description of the invention.

The alcoholates of the invention can be prepared in various manners, butwe prefer the method wherein a triorganotin ester of a lower aliphaticacid is reacted "ice with a zirconium tetraalcoholate whose OR groupscorrespond to those wanted in the finished compound. Where one mol ofthe ester is reacted with one mol of the tetraalcoholate, the resultingcompound has the linkage ESl'lO-ZI'E. Where two mols of the ester arereacted with the tetraalcoholate, the resulting compound has the linkage(ES11--O)2ZI':. These reactions are quantitative and the byproducts arelower aliphatic acid esters of the displaced alcoholate groups. Thus thegeneral formula representing the reaction is as follows:

wherein R, R, R and R" are as identified above, and wherein Acrepresents a monovalent aliphatic acyl group of 1-6 carbons.

The reaction can be carried out by merely heating the reactants togetherin a dry, protective atmosphere or by similarly heating them in thepresence of suitable inert, volatile organic solvent(s). The byproductsof the reactions can be stripped off subsequently along with any solventor portion of any solvent used. The heating to eifect reaction can be atemperature between about 60 and 150 C.

The following examples illustrate the principles of the invention andinclude the best modes presently known to us for practicing theinvention in accordance with those principles.

In the examples, the following abbreviations are sometimes used inequations to identify the indicated radicals:

Me=methyl Pn=isopropyl Bu: butyl Ph=pheny1 EXAMPLE 1 Tributylstannoxyzinconium tri-n-butoxide Zirconium butoxide (0.1 mol) as a 30% solutionin xylene and tributyltin acetate were heated together in a 250 ml.round bottom flask in a protected atmosphere driving off a colorlessliquid which contained both ester and alcohol, finally heating undervacuum at C/0.5 mm. to remove final traces of ester. The residue was aclear light tan liquid, n 1.4892, 61 1.2020 which exhibits mediumabsorption at 6.4-6.7 and strong at 8.7 microns.

Calcd.: Sn, 1925; Zr, 14.79. Found: Sn, 19.15; Zr, 16.07. Molecularweight: 677.8 (Ebullioscopic in benzene). Calcd. monomer: 616.6

The tributyltin acetate used above was prepared in the following manner:

Bu SnOSnBu (CH CO) 0+ 2 Bu SnOOCCH Acetic anhydride 20.4 g. (0.2 mol)was added to tributyltin oxide 119.2 g. (0.2 mol). The reaction isexothermic. Solution takes place at approximately 80 C. and thetemperature was held at C. for 1 hour. The liquid was poured into acrystallizing dish and gave 138 gms. (99%) light yellow solid M.P.83.584.5 C.

Calcd.: Sn, 34.01. Found: Sn, 34.94.

The material can be recrystallized from petroleum ether or hexane.

3 EXAMPLE 2 Tributylstannoxy zirconium triisopropoxide Bu SnOOCCH +Zr(OPr) Using the same general procedure as in Example 1, tributyltinacetate (0.173 mol) and 0.173 mol of tetraisopropyl zirconate wereheated in an oil bath at a pot temperature of 10-5l10 C. Colorless ester14.6 gms. (78.5%) distilled off. Additional 4.0 g. liquid was obtainedby heating under reduced pressure. All fractions, 11 1.3750 showedstrong ester bands in the infrared and alcohol absorptions as well. Thebrown viscous liquid residue, u 1.5165, (1 1.3375 exhibited strongabsorption at 6.4, 8.6 and 9.8 microns.

Calcd. Sn, 20.66; Zr, 15.88. Found: Sn, 20.61; Zr, 20.79. Molecularweight: 1173.7 ebullioscopic (benzene). Calcd. monomer: 574.5.

EXAMPLE 3 Trimethylstannoxy zirconium tributoxide Trimethyltin acetate22.2 g. (0.1 mol) and tetrabutyl-zirconate (0.1 mol) were combined in a100 ml. round bottom flask equipped for distillation and heated under adry atmosphere 1% hours at 140165, then /2 hour to 180 C. During thistime a colorless liquid distilled off leaving as residue a dark coloredliquid which is essentially trimethylstannoxy zirconium tri-n-butoxide.

In the preferred procedure, toluene was used as solvent and byproductester removed by azeotropic distillation. The product was obtained as atoluene solution.

The trimethyltinacetate was prepared in the following manner (70-A-79).

cyclo- Me SnCl NaO O C CH1 ---)h MeaSnO CCHa NaCl exane Trimethyltinchloride (0.2 mol) dissolved in 100 ml. cyclohexane was added over a2-hour period to a heated suspension of 28.7 g. (0.35 mol) sodiumacetate in 750 ml. cyclohexane. Reaction was refluxed an additional hourafter completion of addition. The precipitate was filtered through alarge Buchner funnel. The filtrate was evaporated but contained noproduct. Repeated soxhlet extraction of the filter cake gave 33.0 gms.(75%) product which sublimes at 190-195 C. in a sealed tube.

Calcd. for C H O Sn: Sn, 53.4; Sap. No. 251. Found:

Sn, 52.84; Sap. No. 248

In a more desirable preparation xylene was used as solvent and filteredhot after completion of the reaction. Upon cooling, the xylene depositspure trimethyltin acetate in 92% yield.

EXAMPLE 4 Triphenylstannoxy zirconium trlisopropoxide Triphenyltinacetate (0.1 mol) and tetraisopropyl zirconate (0.1 mol) were combinedin toluene under dry conditions and refluxed for two hours. Toluene andbyproduct isopropyl acetate were slowly removed by distillation througha 30 cm. packed column maintaining the toluene level in the reactionvessel by addition of toluene. The distillation was continued until onlypure toluene appeared as distillate. The residual solution containedessentially triphenylstannoxy zirconium triisopropoxide. A two percentsolution imparts Water repellency to paper.

4 EXAMPLE 5 Triphenylstannoxy zirconium tributoxide Ph snoH+zr(oBu),- PhSnOZr(OBu) -+BuOH Purified triphenyltin hydroxide (0.1 mol) andtetrabutylzirconate (0.1 mol) as a 30% solution in xylene were heatedtogether for 2 /2 hours at 60 C. pot temperature in an inert atmosphere.Vacuum (0.1-4 mm.) was applied and solvent and byproduct alcohol removedover a 2-hour period maintaining the bath temperature at 60-80 C. Theresidual liquid consisted essentially of triphenylstannoxy zirconiumtributoxide.

EXAMPLE 6 Tributylstannoxy zirconium tributoxide (0.1 mol) was reactedwith 2-ethylhexanol (0.1 mol) in refluxing toluene and the reactiondriven to completion by removal of byproduct butanol as a tolueneazeotrope. The product was obtained as a toluene solution and was aneffective water repellent at 2% concentration.

EXAMPLE 7 Tributylstannoxy zirconium tributoxide (0.1 mol) anddiethanolamine (0.1 mol) were reacted in toluene by the same procedureas described in Example 6. The resultant solution contains thediethanolamine zirconate product and it is assumed to be partiallypolymeric.

EXAMPLE 8 Tributylstannoxy diisopropoxy zirconium perfluorooctanoate (A)This derivative may be prepared by either of two methods:

Bu3SnOZr(OPr)a rrooo c1=. .cr

Method 2 is the preferred method and the reaction is generally conductedin solvent. When the product is to be used as a water or oil repellentor as a textile finish, the product is not isolated but used directly asa solution in the desired hydrocarbon after dilution.

Tetrapropylzirconate (0.1 mol) and perfluorooctanoic acid were combinedin 600 ml. toluene and the mixture was refluxed for two hours. Toluenewas then distilled through a 30 cm. packed column to remove thebyproduct alcohol as an azeotrope. Thereafter, tributyltin acetate isadded (0.1 mol) and the process is repeated. When all the propylacetateis removed by azeotropic distillation, the product is essentiallytributylstannoxy diisopropoxy zirconium perfluorooctanoate and is usedas a solution after dilution to the proper concentration.

In the manner of Method 1, the triorganostannoxy zirconium alcoholatesof the invention can be reacted with higher alcohols, glycols,aminoalcohols, fluorohydrocarbyl alcohols, and the corresponding acidsto prepare desired derivatives.

EXAMPLE 9 The compound prepared in Example 1 (tributylstannoxy zirconiumtri-n-butoxide) was used in standard Waterrepellency tests. Thefollowing table summarizes the results.

TABLE I.WATE R-REPELLENCY TESTS 1 Special handsheets containing 75%hardwood pulp and 25% softwood pulp are prepared in the PaperLaboratory. A 3% x 7 sheet of this paper is dipped into the waterrepellent solution, removed and rolled tree of excess solvent with ahard rubber roller on a glass surface. The handsheets are then air driedand conditioned at 73 F. and 50% relative humidity for one day. Thetreated paper is placed under the surface of a reservoir of water in theTwing- Albert Fotosize Penetration Tester and the number of secondsrequired to effect wetting or penetration is recorded. This time isautomatically recorded by a timer shut-oil actuated by minimum lighttransmittance through the paper. Feathering ink, aqueous base, oraqueous acid can be substituted for the plain water. Feathering ink isprepared by combining: 6 grams blue dye (National 2 BEX); 250 ml. waterat 120 F.; 6 ml. hydrochloric acid. Cool to 70 F. and dilute to a totalvolume of 950 ml.

2 TAPPI Standards and Suggested Methods; T441 M-60; (TechnicalAssociation of the Pulp and Paper Industry). A five-minute exposure testis used, and the Weight of water absorbed per square meter of paper isreported. Paper can be 0.0004 mil and over in thickness.

3 In pounds per 3.000 square feet.

4 Applied to paper in the form of 2% (wt.) solutions in toluene.

EXAMPLE (Table IX of Part VII) The compound of Example 1 was screenedfor fungicidal activity by the serial dilution technique. The comisrecorded as rise time. A control catalyst, stannous 0 octoate, gives arise time of 50-90 seconds.

Wt. in Rise Max. Catal st pound was tested aga nst each of six fungl.The range of M atmal Grams Tim C 01M Internal Raflgg compoundconcentration, expressed as percent active in- (890,) Temp, C gredient,was .007i8% through 0.000015%. All tests were Com p of 11x. 1 0. 8 77White 116 Excellent. performed in Difco Sabourand L1qu1d Medium at 25 C.Comp ofEx. 1 0.4 100 do 115 Good. The tests were incubated for sevendays.

We claim:

Fungus Eu SnOZr(0Bu)aMinimum 1. The polymeric reaction product formedfrom the Inhlbltory Concentmmn (Percent) reaction of dialkanolamine withtriorganostannoxy Aspergillus niger 0 000125 zirconium compoundsselected from the group consist- Botrytis ullii 0 000031 in ofChaetomium glabosurrr.-- 0 000004 g Glomerella cingulata 0 000062 R0 R0Pullularia pullulams... 0 00025 Pemczllzu'm italzcum 0 0 0 1 I; and

EXAMPLE 11 2 The compound of Example 1 was tested as a urethane whereinR R and R" can be like or difiercnt C alkyl, alkenyl or phenyl radicals,and wherein X is an foam catalyst. 40

To prepare the foams, 200 grams of polyethcr resin 1 g i ifg g gi gfislald X radlcal bemg C148 alkyl or are weighed into a paper drinking cupand 3.0 grams 2 The roduct i 1 h h d (3.25 ml. of silicone oil'(dimethyl polysiloxane) and di i 1 th w erem Sal y foxy 0.64.0 g. ofcatalyst are added and mixed for two mina y amme 1s 16 am amine uteswith a 3-prop Lightnin mixer.

Diethylene triaminc (0.2 gram) and N-ethylmorpholine References Clted(0.3 gram) are dissolved in 7.4 grams water in a small UNITED STATESPATENTS beaker. This mixture is combined with the polyether mix2,580,473 1/1952 s 260.4293 and strirrcd for one minute. 2,845,4457/1-958 Russell 2-60-4293 Toluene diisocyanatc (96.4 grams) is pouredinto the 2,894,966 7/1959 R ll 250 429 above mix while stirring andmixed for seven seconds 3,307,973 3/1967 Gibb 25() 429 3 while rotatingthe cup. The cup is dropped while stirring 3,334,119 8/1967 C h 2 0 4293 and with the same motion poured rapidly into a 12" x 12 carton. TOBIASE. LEVOW, Primary Examiner.

The stopwatch is started at the time of pouring and the time in secondsfor the foam to obtain maximum rise Niaz 'lriol LG 56 (T.M.) glycolpolyether resin having an average molecular weight of about 3000, anaverage hydroxyl number (mg. KOH per gram) of 5'6.

H. M. S. SNEED, Assistant Examiner.

US. Cl. X.R.

